Composition comprising ethylene copolymers and polyolefin

ABSTRACT

Disclosed are compositions of ethylene/(meth)acrylate copolymers, polyolefins (e.g., polyethylene and polypropylene), optional tackifier resins and optional fillers that provide very strong, tight hermetic heat seals yet are easily peelable. These compositions are useful as an adhesive layer in multilayer structures that are useful as packaging lidding films. Also disclosed are packages that comprise these multilayer structures.

The application claims the priority to U.S. provisional application No.60/535,107, filed Jan. 8, 2004, 60/540,238, filed Jan. 29, 2004, and60/588,230, filed Jul. 15, 2004, the entire disclosure of eachprovisional application is incorporated herein by reference.

The invention relates to a composition comprising a polyolefin (e.g.,polyethylene and polypropylene) and an ethylene copolymer, to amultilayer structure comprising the composition, and to a packagecomprising the multilayer structure.

BACKGROUND OF THE INVENTION

The packaging industry uses a wide variety of films and containersprepared from various thermoplastic resins and compositions forpackaging food and non-food products. These packages provide adequateprotection (for example, protection from mechanical damage, barriers toair or moisture, etc.) of the product contained within until theconsumer is ready to use the product. It is also desirable for thepackage to be designed to allow the consumer easy access to the productat the appropriate time. Often, packages consist of rigid containersmade from metal (particularly aluminum), paper, fiberboard or plastic(for example, polypropylene, crystallized polyethylene terephthalate(CPET) and high-impact polystyrene (HIPS)) with a lidding film sealed tothe container. It is desirable that the seal between the container andthe lidding film provide a strong hermetic seal to protect the productand that the seal is easily and cleanly peeled by the consumer.

Common compositions used for sealants for lidding include compositionscomprising polypropylene, polyethylene, ethylene vinyl acetatecopolymers (EVA), ethylene/(meth)acrylate copolymers or amorphouspolyester. They can also contain fillers or additives for achieving aneasy peel characteristic. Many compositions comprising polyolefins arecurrently used for peelable heat seals in packaging applications becauseof their good processibility, low cost, and adequate adhesion for manyapplications. However, these compositions are not sufficiently robustfor all applications. For example, many packages are refrigerated orfrozen to help preserve the product therein, and it is desirable toretain seal strength in cold temperatures. Also, polyolefin compositions(for example, those that contain EVA) have limited heat resistance thatrestricts their ability to be processed at high temperatures.

Therefore, it is desirable to develop compositions that provide improvedperformance than currently provided by commercially available sealants.

SUMMARY OF THE INVENTION

The invention provides a composition comprising or consistingessentially of or produced from (a) from about 10 to about 80 weight %of at least one ethylene copolymer; (b) from about 5 to about 60 weight% of at least one polyolefin; (c) from 0 to about 35 weight % of atleast one tackifying resin; and (d) from 0 to about 35 weight % offiller. The ethylene copolymer refers to ethylene/(meth)acrylatecopolymer, ethylene/alkyl acrylate copolymer, ethylene/(meth)acrylicacid copolymer, ethylene/alkyl acrylic acid copolymer, an ionomerthereof, or combinations of two or more thereof.

The invention also provides a multilayer structure comprising orproduced from at least one layer of the composition disclosed above andat least one additional layer comprising foil, paper, polyester,polyamide, polyolefin, polyethylene vinyl alcohol, polyethylene vinylacetate, ethylene copolymer or ionomer thereof, polyvinyl chloride,polyvinylidene chloride, or anhydride-modified polyolefin.

The invention further provides a package comprising or produced from thecomposition and multilayer structure disclosed above.

The invention also provides a package comprising (1) a containercomprising a structure comprising at least one layer of foil,paperboard, glass, high-density polyethylene (HDPE), polypropylene (PP),high-impact polystyrene (HIPS), expanded polystyrene (EPS), acrylichomopolymer or acrylic copolymer, polycarbonate, polysulfone, amorphouspolyethylene terephthalate (APET), crystalline polyethyleneterephthalate (CPET), polyvinyl chloride (PVC),polychlorotrifluoroethylene (PCTFE), polyacrylonitrile homopolymer orcopolymer, polyacetal, or polyacetal copolymer; and (2) a peelable lidcomprising a multilayer structure disclosed above.

DETAILED DESCRIPTION OF THE INVENTION

All references disclosed herein are incorporated by reference.

The term “(meth)acrylic acid” means methacrylic acid and/or acrylicacid. Likewise, the term “(meth)acrylate” means methacrylate and/oracrylate.

Thermoplastic compositions are polymeric materials that can flow whenheated under pressure. Melt index (MI) is the mass rate of flow of apolymer through a specified capillary under controlled conditions oftemperature and pressure. Melt indices reported herein are determinedaccording to ASTM 1238 at 190° C. using a 2160 g weight, with values ofMI reported in g/10 minutes. The thermoplastic compositions are suitablefor preparation of films and multilayer structures by extrusionprocessing.

The term “foil” refers to a thin, flexible film or sheet of metal, suchas aluminum. It also refers to multilayer structures in which at leastone layer of aluminum is adhered to additional layers of othermaterials, provided at least one exterior layer of the multilayerstructure is a layer of aluminum.

Peelable heat seals commonly can be designed to have three differentfailure modes when peeling seal to seal or seal to differentiatedsubstrate. Failure can be interfacial, delamination or cohesive whenpeeling one from the other under stress at various angles of peel andspeeds. Interfacial seals are designed to fail at the heat sealinterface of the selected sealing surface (i.e., the sealant layer peelscleanly away from the substrate layer). In most cases seal strength isdetermined by temperature, pressure and dwell time. Seals that do notpeel cleanly can contaminate the contents of the package with fragmentsof the seal or lidding. Interfacial peelable seals are desirable toprevent such contamination. Delamination heat seals are designed to failat an internal interface of a multilayer film structure. This designedfailure interface is in a chosen layer somewhere behind the actual heatseal layer in the film structure. Thickness and adhesion to the choseninternal layer interface will determine strength of the seal duringpeeling. In this case the entire sealant layer transfers to thesubstrate as the film structure is being peeled away. Cohesive sealfailure by design fails within the actual sealant layer itself. Whenpeeling the seal under stress and speed, the seal layer itself splitswithin and transfers a portion of the sealant material to the sealantsubstrate. Internal strength of the sealant material is the determiningfactor for actual strength of the heat seal.

The composition can include or consist essentially of (a) from about 10to about 80 weight % of at least one ethylene/alkyl (meth)acrylatecopolymer; (b) from about 5 to about 60 weight % of at least onepolyolefin; (c) from about 0.5 to about 35 weight % of at least onetackifying resin; and (d) from 0 to about 35 weight % of filler.

The composition can also comprise or consist essentially of or beproduced from (a) from about 40 to about 80 weight % of at least oneethylene/alkyl (meth)acrylate copolymer; (b) from about 20 to about 60weight % of at least one polyolefin. The composition can also consistessentially of (a) from about 10 to about 80 weight % of at least oneethylene/alkyl (meth)acrylate copolymer; (b) from about 20 to about 60weight % of at least one polyolefin; and (c) from about 10 to about 20weight % of at least one tackifying resin or (a) from about 40 to about60 weight % of at least one ethylene/alkyl (meth)acrylate copolymer; (b)from about 20 to about 40 weight % of at least one polyolefin; (c) fromabout 10 to about 20 weight % of at least one tackifying resin; and (d)from about 5 to about 20 weight % of filler.

The terms “ethylene copolymer” means a thermoplastic copolymer derivedfrom the copolymerization of ethylene monomer and at least one alkylacrylate or alkyl methacrylate comonomer, wherein the alkyl groupcontains from 1 to 8 carbon atoms. Ethylene/alkyl (meth)acrylatecopolymer and ethylene/(meth)acrylate copolymer are used interchangeablyherein. For example, alkyl acrylates include methyl acrylate, ethylacrylate and butyl acrylate. “Ethylene/methyl acrylate (EMA)” means acopolymer of ethylene (E) and methyl acrylate (MA). “Ethylene/ethylacrylate (EEA)” means a copolymer of ethylene (E) and ethyl acrylate(EA). “Ethylene/butyl acrylate (abbreviated EBA)” means a copolymer ofethylene (E) and butylacrylate (BA).

The amount of the alkyl acrylate comonomer incorporated into theethylene/(meth)acrylate copolymer can, in principle, vary broadly fromabout 1 weight percent to as high as 40 weight percent of the totalcopolymer or even higher. The choice of the alkyl group can be methylgroup up to an eight-carbon atom alkyl group with or without branching.For example, the alkyl group in the alkyl (meth)acrylate comonomer usedto prepare the ethylene copolymer can be from one to 4 carbon atoms andthe alkyl (meth)acrylate comonomer can have a concentration range offrom 5 to 30, or 9 to 27 weight percent, of the totalethylene/(meth)acrylate copolymer. Methyl acrylate (the most polar alkylacrylate comonomer) can be used to prepare an ethylene/methyl acrylatedipolymer. The methyl acrylate comonomer can be present in aconcentration range of from 5 to 30, 9 to 25, or 9 to 24 weight %, ofthe ethylene copolymer.

A mixture of two or more ethylene copolymers can be used as component(a) in the compositions in place of a single copolymer. Particularlyuseful properties may be obtained when two properly selectedethylene/alkyl acrylate copolymers are used in blends. For example butnot limitation, compositions include those wherein the ethylene/alkylacrylate component comprises two different ethylene/methyl acrylatecopolymers. Also for example, one may replace a single EMA grade in ablend with an equal amount of a properly selected mixture of two EMAgrades, where the mixture has the same weight percent methyl acrylatecontent and melt index as the single EMA grade replaced. By combiningtwo different properly selected EMA copolymer grades, modification ofthe properties of the composition may be achieved as compared withcompositions containing only a single EMA resin grade.

The ethylene/alkyl (meth)acrylate copolymers may also optionally includeat least one additional comonomer including (meth)acrylic acid, maleicanhydride, glycidyl methacrylate and carbon monoxide to form terpolymerssuch as ethylene/isobutyl acrylate/methacrylic acid, ethylene/methylacrylate/maleic anhydride, ethylene/butyl acrylate/glycidyl methacrylate(EBAGMA) and ethylene/butyl acrylate/carbon monoxide (EBACO).

Ethylene/(meth)acrylate copolymers can be prepared by processes wellknown in the polymer art using either autoclave or tubular reactors. Thecopolymerization can be run as a continuous process in an autoclave. Forexample, ethylene, an alkyl (meth)acrylate such as methyl acrylate, andoptionally a solvent such as methanol (see, e.g., U.S. Pat. No.5,028,674) are fed continuously into a stirred vessel such as autoclaveof the type disclosed in U.S. Pat. No. 2,897,183, together with aninitiator. The rate of addition may depend on polymerizationtemperature, pressure, and concentration of methyl acrylate monomer inthe reaction mixture needed to achieve the target composition of thecopolymer. In some cases, it may be desirable to use a telogen such aspropane, to control the molecular weight. The product mixture can becontinuously removed from the vessel. After the product mixture leavesthe reaction vessel, the copolymer can be separated from the unreactedmonomers and solvent (if used) by conventional means, e.g., vaporizingthe nonpolymerized materials and solvent under reduced pressure and atan elevated temperature. Autoclave acrylate copolymers are availablefrom Voridian under the name EMAC and from ExxonMobil under the nameOptema and from Atofina under the name of Lotryl.

Tubular reactor produced ethylene/(meth)acrylate copolymer can bedistinguished from the more conventional autoclave producedethylene/(meth)acrylate as generally known in the art. Thus the term orphrase “tubular reactor produced” ethylene/(meth)acrylate copolymerdenotes an ethylene copolymer produced at high pressure and elevatedtemperature in a tubular reactor or the like, wherein the inherentconsequences of dissimilar reaction kinetics for the respective ethyleneand alkyl (meth)acrylate (e.g. methyl acrylate) comonomers is alleviatedor partially compensated by the intentional introduction of the monomersalong the reaction flow path within the tubular reactor. As generallyrecognized in the art, such a tubular reactor copolymerization techniquewill produce a copolymer having a greater relative degree ofheterogeneity along the polymer backbone (a more blocky distribution ofcomonomers), will tend to reduce the presence of long chain branchingand will produce a copolymer characterized by a higher melting pointthan one produced at the same comonomer ratio in a high pressure stirredautoclave reactor.

Tubular reactor produced ethylene/(meth)acrylate copolymers of thisnature are commercially available from E. I. du Pont de Nemours andCompany (DuPont), Wilmington, Del.

The manufacturing of the tubular reactor ethylene/(meth)acrylatecopolymers in a high pressure, tubular reactor at elevated temperaturecan include additional introduction of reactant comonomer along the tubeand not merely manufactured in a stirred high-temperature andhigh-pressure autoclave type reactor. Similar ethylene/(meth)acrylatecopolymeric material can be produced in a series of autoclave reactorswhere comonomer replacement is achieved by multiple zone introduction ofreactant comonomer as disclosed in U.S. Pat. Nos. 3,350,372; 3,756,996;and 5,532,066, and as such these high melting point materials can beconsidered equivalent to tubular reactor produced copolymers forpurposes of this invention. These products are available from Voridianunder the name EMAC+ or EBAC+.

To further illustrate and characterize the tubular reactor producedethylene/alkyl acrylate copolymer relative to conventional autoclaveproduced copolymer, the following list of commercially availableethylene/methyl acrylate copolymers with associated melting point datashow that tubular reactor produced EMA resins have considerably highermelting points versus autoclave EMA's due to a very different MAdistribution along polymer chains:

Autoclave Produced Copolymers

ExxonMobil, N.J.; EMA (21.5 wt % MA) mp=76° C.

ExxonMobil, N.J.; EMA (24 wt % MA) mp=69° C.

Atofina, France; EMA (20 wt % MA) mp=80° C.

Atofina, France; EMA (24 wt % MA) mp=73° C.

Tubular Eeactor Produced Copolymers

DuPont EMA (25 wt % MA) mp=88° C.

DuPont EMA (20 wt % MA) mp=95° C.

For additional discussion regarding the differences between tubularreactor produced and autoclave produced ethylene/alkyl acrylatecopolymers, see Richard T. Chou, Mimi Y. Keating and Lester J. Hughes,“High Flexibility EMA made from High Pressure Tubular Process”, AnnualTechnical Conference—Society of Plastics Engineers (2002), 60th(Vol. 2),1832-1836. CODEN: ACPED4 ISSN:0272-5223; AN 2002:572809 CAPLUS.

Ethylene/alkyl acrylate copolymers suitable for use in this inventionare available from DuPont. See Table A for specific examples ofethylene/alkyl acrylate copolymers available from DuPont. TABLE AEthylene Alkyl Alkyl acrylate Melt Flow Acrylate Copolymer wt % (g/10min) EMA-1 25 0.4 EMA-2 25 0.6 EMA-3 9 2 EMA-4 14 2 EMA-5 18 2 EMA-6 242 EMA-7 9 6 EMA-8 20 8 EMA-9 13 9 EEA-1 12 1 EEA-2 16 1 EEA-3 15 6 EEA-415 7 EBA-1 7 1.1 EBA-2 7 1.1 EBA-3 17 1.5 EBA-4 17 1.8 EBA-5 27 4 EBA-617 7

The ethylene/(meth)acrylate copolymers available for use can vary inmolecular weight, indicated by the range of melt index (MI), numericallyin terms of a fraction up to about 10, provided in Table A. The specificselection of the MI grade of polymer component(s) to be used may beinfluenced by the process used to create the multilayer structure.Preferred are ethylene copolymers having MI's from about 0.1 to about100 g/10 min., or from about 0.5 to about 50, or from about 0.50 toabout 30 g/10 min.

Polyolefins can include homopolymers and copolymers of olefins havingfrom 2 to 8 carbon atoms. Examples of polyolefins include polyethylenehomopolymers, polypropylene homopolymers, copolymers comprisingethylene, and copolymers comprising propylene. Polyethylenes (PE) can beprepared by a variety of methods, for example but not limitation, thewell-known Ziegler-Natta catalyst polymerization (see e.g., U.S. Pat.Nos. 4,076,698 and 3,645,992), metallocene catalyst polymerization (see,e.g., U.S. Pat. No. 5,198,401 and 5,405,922), Versipol® catalystpolymerization and by free radical polymerization. The polymerizationcan be conducted as solution phase processes, gas phase processes, andthe like. Polyethylenes can include linear polyethylenes such as highdensity polyethylene (HDPE), linear low density polyethylene (LLDPE),very low or ultralow density polyethylenes (VLDPE or ULDPE) and branchedpolyethylenes such as low density polyethylene (LDPE). The densities ofPE suitable for use in the present invention range from about 0.865 g/ccto about 0.970 g/cc. A polyethylene of note is a copolymer of ethyleneand 1-butene. Such a copolymer with 12.6 weight % 1-butene, having amelt index of 3.5 is available as Exact® 3035 from ExxonMobil. Anotherpolyethylene of note is a copolymer of ethylene and 1-octene. Such acopolymer with 12 weight % octene, having a melt index of 3.5 isavailable as Engage® 8450 from DuPont Dow Elastomers.

Polypropylene (PP) polymers include homopolymers, random copolymers,block copolymers and terpolymers of propylene. Copolymers of propyleneinclude copolymers of propylene with other olefins such as ethylene,1-butene, 2-butene and the various pentene isomers, etc. and preferablycopolymers of propylene with ethylene. Terpolymers of propylene includecopolymers of propylene with ethylene and one other olefin. Randomcopolymers, also known as statistical copolymers, are polymers in whichthe propylene and the comonomer(s) are randomly distributed throughoutthe polymeric chain in ratios corresponding to the feed ratio of thepropylene to the comonomer(s). Block copolymers are made up of chainsegments consisting of propylene homopolymer and of chain segmentsconsisting of, for example, random copolymer of propylene and ethylene.The term “polypropylene” refers to any or all of the polymers comprisingpropylene described above.

Homopolymers and random copolymers can be manufactured by any knownprocess. For example, polypropylene polymers can be prepared in thepresence of catalyst systems of the type known as Ziegler-Natta, basedon organometallic compounds and on solids containing titaniumtrichloride. Block copolymers can be manufactured similarly, except thatpropylene is generally first polymerized by itself in a first stage andpropylene and additional comonomers such as ethylene are thenpolymerized, in a second stage, in the presence of the polymer obtainedduring the first. Each of these stages can be carried out, for example,in suspension in a hydrocarbon diluent, in suspension in liquidpropylene, or else in gaseous phase, continuously or noncontinuously, inthe same reactor or in separate reactors. Additional informationrelating to block copolymers and to their manufacture may be foundparticularly in chapters 4.4 and 4.7 of the work “Block Copolymers”edited by D.C. Allport and W. H. Janes, Applied Science Publishers Ltd(1973).

The polyolefins can also be modified by the incorporation of low levels(typically less than about 3 weight %) of one or more polar monomersincluding, for example but not limitation vinyl acetate, alkylacrylates, carbon monoxide, glycidyl methacrylate, (meth)acrylic acidand maleic anhydride. The incorporation of these polar comonomers can beaccomplished by copolymerization or by grafting.

Blends of two or more polyolefins can be used. For example, LLDPE can beblended with either LDPE or HDPE to provide polyethylene blends or ablend of PP and poly(1-butene) (PB).

The composition may optionally contain tackifying resins. Any tackifier,also referred to as adhesive, known to one skilled in the art such asthose disclosed in U.S. Pat. No. 3,484,405 can be used. Such tackifiersinclude a variety of natural and synthetic resins and rosin materials.The resins can be liquid, semi-solid to solid, or solid, includingcomplex amorphous materials generally in the form of mixtures of organiccompounds having no definite melting point and no tendency tocrystallize. Such resins may be insoluble in water and can be ofvegetable or animal origin, or can be synthetic resins. The resins canprovide substantial and improved tackiness to the composition. Suitabletackifiers include, but are not limited to, para-coumarone-indeneresins, terpene resins, butadiene-styrene resins, polybutadiene resins,hydrocarbon resins, rosins, and combinations of two or more thereof.

Generally the coumarone-indene resins have a molecular weight rangingfrom about 500 to about 5,000. Examples of resins of this type that areavailable commercially include those materials marketed as “Picco”-25and “Picco”-100.

The terpene resins include styrenated terpenes and can have a molecularweight ranging from about 600 to 6,000. Examples of commerciallyavailable resins are marketed as “Piccolyte” S-100, as “StaybeliteEster” #10 (Eastman Chemical, Kingsport, Tenn.), which is a glycerolester of hydrogenated rosin, and as “Wingtack” 95, which is apolyterpene resin. A terpene resin-based tackifier of note is derivedfrom poly-limonene, a monomer recovered from the citrus industry,available as Piccolyte® C115 from Pinova.

The butadiene-styrene resins can have a molecular weight ranging fromabout 500 to about 5,000. Example of commercial product is marketed as“Buton” 100, a liquid butadiene-styrene copolymer resin having amolecular weight of about 2,500.

The polybutadiene resins can have a molecular weight ranging from about500 to about 5,000. A commercially available example is that marketed as“Buton” 150, a liquid polybutadiene resin having a molecular weight ofabout 2,000 to about 2,500.

A hydrocarbon resin can be produded by catalytic polymerization ofselected fractions obtained in the refining of petroleum, and can have amolecular weight ranging from about 500 to about 5,000. Examples of suchresin are those marketed as “Piccopale”-100, and as “Amoco” and“Velsicol” resins. Similarly, polybutenes obtained from thepolymerization of isobutylene may be included as a tackifier.

The tackifier may also include rosin materials, low molecular weight(such as, for example, 1300) styrene hard resins such as the materialmarketed as “Piccolastic” A-75, disproportionated pentaerythritolesters, and copolymers of aromatic and aliphatic monomer systems of thetype marketed as “Velsicol” WX-1232. The rosin that may be employed inthe present invention may be gum, wood or tall oil rosin but preferablyis tall oil rosin. Also the rosin material may be modified rosin such asdimerized rosin, hydrogenated rosin, disproportionated rosin, or estersof rosin. Esters can be prepared by esterifying the rosin withpolyhydric alcohols containing from 2 to 6 alcohol groups.

Another tackifier resin of note is Regalite R1125 (a hydro carbon)available from Eastman Chemical.

A more comprehensive listing of tackifiers, can be found in the TAPPI CAReport #55, February 1975, pages 13-20, a publication of the TechnicalAssociation of the Pulp and Paper Industry, Atlanta, Ga., which listswell over 200 tackifier resins that are commercially available.

The tackifier may be either combined directly with the ethylenecopolymer or other components disclosed; or pre-melt compounded into amasterbatch formulation. Such technology is described in U.S. Pat. No.6,255,395 and JP 2002 173,653, entire disclosures of both areincorporated herein. For example, poly-limonene may be blended with anethylene/octane copolymer to prepare a tackifier masterbatch that can beadded to the remaining components of the composition in a subsequentblending operation.

Two or more individual tackifiers can be blended.

The compositions of this invention may also optionally contain fillers.Addition of fillers can increase the temperature resistance and affectpeel seal characteristics of the composition.

A filler can comprise particles of inorganic compounds, such as mineralsand salts. The filler can be included in the composition on a weightbasis as a function of the density of the filler. Particle size andshape of the filler also may have an effect on properties of blends.Fine particle size fillers generally have a tendency to result in higherblend viscosities and they are also more expensive. No. 9 Whiting (about95% through 325 mesh) represents a viable midpoint in coarseness,availability, and cost. More preferred fillers are calcium carbonate andtalc (essentially Mg₃Si₄O₁₀(OH)₃), and most preferred is talc. Theamount of filler present in the composition of the present invention canbe from about 0.001 to about 30 weight %.

Fillers may be pre-blended with an ethylene/alkyl acrylate or polyolefinin a masterbatch prior to blending into a composition of this invention.For example, talc may be blended with ethylene/methyl acrylate (20weight % MA) copolymer to prepare a filler masterbatch that can be addedto the remaining components of the composition in a subsequent blendingoperation.

Fillers may also be polymeric materials that are not fully compatiblewith the combination of ethylene/alkyl (meth)acrylate of component (a)and the polyolefin of component (b) such as, for example, polystyrenicresins, referring to homopolymers of styrene or α-methylstyrene orcopolymers of styrene with unsaturated monomers such as, but not limitedto ethylene, butene, butadiene, or isoprene. Specific examples include,but are not limited to ethylene/styrene random or block copolymers,ethylene/butadiene random or block copolymers and hydrogenated andpartially hydrogenated butadiene/styrene copolymers. Also useful arepolystyrenics further modified for enhanced impact properties andusually referred to as High Impact Polystyrene or HIPS. Blends andmixtures of polystyrenics may be used. Specific examples include but arenot limited to, HIPS from Nova Chemicals or ethylene/styrene copolymerssold by Dow Chemical.

Other additives can be present such as antioxidants and thermalstabilizers, ultraviolet (UV) light stabilizers, colorants, pigments anddyes, fillers, delustrants, anti-slip agents, plasticizers, anti-blockagents, compatiblizers, components for modifying surface characteristicssuch as Coefficient of Friction (COF), anti static and anti fog agents,other processing aids and the like. These additives may be present inthe compositions in quantities that are generally from 0.001 to 20, orfrom 0.01 to 15 weight %, so long as they do not detract from theadhesion functionality of the composition (the weight percentages ofsuch additives are not included in the total weight percentages of thecomposition as defined above in the Summary of the Invention).Typically, many such additives may be present in from 0.01 to 5 weight%. Of note are antioxidants that may be present in from 0.01 to 1 weight%. Antioxidants are available under the trade name Irganox from CibaGeigy Inc., Tarrytown, N.Y. For example, phenolic antioxidants such asIrganox E201, CAS Number 10191-41-0) or its derivatives may be added tothe composition. Irganox 1010, CAS Number 6683-19-8, is anotherantioxidant suitable for use in this invention. Also of note areadditives for modifying surface characteristics such as coefficient offriction, for anti-blocking or for chill roll release that may bepresent in amounts from 0.001 to 5 weight %. For example, such anadditive is a dispersion of silicon dioxide (2 weight %) in anethylene/methacrylic acid copolymer used as carrier concentrate forblending into a resin (available from DuPont as Conpol® 20B).

The optional incorporation of such additives into the compositions canbe carried out by any known process, for example, by dry blending,extruding a mixture of the various constituents, the conventionalmasterbatch technique, or the like.

The adhesive resin composition of this invention may be produced bymixing predetermined amounts of the ethylene/(meth)acrylate copolymercomponent (a), the polyolefin (b) optionally the tackifier (c), andoptionally the filler (d) by a mixer such as a Henschel mixer, a Vblender, a ribbon blender or a tumbler blender; or after mixing,melt-kneading the mixture by a single screw extruder, a twin screwextruder, a kneader, a Banbury mixer, etc. and then pelletizing, meltextruding, granulating or pulverizing the mixture.

Upon proper melt blending or heat mixing, the composition can beextruded through a die via coextrusion. The thickness of the extrudedsealant is preferably about 1 to 400 microns, more preferably 5 to 100microns, yet more preferably 10 to 30 microns.

Alternatively, the compositions of the present invention can be extrudedinto a film having a thickness of about 1 to 100 microns, morepreferably 5 to 100 microns and yet more preferably 10 to 75 microns andsubsequently laminated to paper, foil, or film as part of a multilayerstructure.

The adhesive resin composition of this invention can be used to bondvarious substrates or polymers to each other. Typically, the articlesare bonded or adhered by heat seal.

The final adhesive composition can be used directly, for example in amelt coextrusion, or it can be extruded in rope or pellet form orreduced to a chip or powder form for use in an appropriate applicator.It can be cast or extruded into a film or web form for subsequent use.In such shaped forms, it can be placed between the substances to bebonded and then activated by heat and pressure. The adhesives can beapplied by any of the hot melt applicators commonly used.

Although these compositions can be applied in any thickness thepractitioner finds expedient, it is preferred to employ layer thicknessof from 0.0002 mils to 10 mils (0.0000005-0.025 cm).

The invention further provides a seal or laminate suitable forapplication to containers, packages, films and the like by heat sealing,which has a good heat sealing property and can be easily peeled.

Films and coatings can be made from the compositions and laminated orcoated onto other films or structures. Alternatively, the compositioncan be simultaneously coextruded with other materials. To summarize, theadhesive resin compositions disclosed here have utility due to chemicaland physical properties as bonding agents and adhesives to provideso-called peel and seal adhesives and can be used in forms such asadhesive sheets, tapes, or laminated products.

The compositions can also be useful in providing heat seals for sealingto polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), PP,polyethylene terephthalate (PET) and polystyrene where peelable sealsare desired. The compositions can provide wide levels of seal strengthrange and a broader, higher-temperature operating window over existingheat sealable systems.

Existing alternative sealant systems are solvent-borne systems generallybased on EVA or amorphous PET and applied by roller or gravure systemsto a carrier web. These coatings are generally very thin and are limitedto ingredients that are soluble in solvent systems. The invention is notlimited by sealant layer thickness or combination of components to gainthe desired heat seal strength or peelability desired. The sealantdisclosed here can be free of solvent and address environmental concernsregarding solvent use. No-solvent sealing systems can be simpler andoffer more flexibility, which may improve economics in manufacturing ofthe finished sealant web.

The invention also includes an improved heat sealable material toprovide peelable, hermetic seals at a wide range of seal strengths tocontainers made from PCTFE fluoropolymers (a number of homopolymers andcopolymers derived from polymerization of chlorotrifluoroethylene areavailable commercially under the tradename Aclar® from Honeywell, Inc.,Morristown, N.J.). PCTFE may provide high moisture and oxygen barrierproperties, allowing greater shelf life of the product packaged. PCTFEfluoropolymers provide barrier properties comparable to foil. Use ofPCTFE may be limited if a composition cannot provide good adhesion tofluoropolymers such as PCTFE.

A PCTFE layer can be adhered directly to a second layer of PVC to createthe structure from which the container is formed. The PVC is used as thesealing surface as it has high affinity to many heat sealable materials.It also provides bulk to the structure, as it is less expensive than thePCTFE. Both materials provide high clarity and formability. PVC as theseal surface may have insufficient oxygen and moisture barrierproperties. When the top barrier sealant web is heat sealed to the PVC,the barrier properties of the PCTFE cannot be fully realized. Oxygen andmoisture permeate through the PVC between the heat-sealable liddingmaterial and the PCTFE, leading to shortened shelf life.

The PCTFE can become the innermost layer and seal substrate for the heatsealable top web, allowing the final package to realize the full barrierproperties of the PCTFE, leading to longer shelf life. Also, not as muchthinning of the PCTFE occurs in the forming process by making the PCTFEthe inside layer instead of the outside layer. This can allow for a highbarrier, peelable lidding that provides an easily opened, transparentpackage with improved shelf life.

The sealant materials disclosed here can be useful to the pharmaceuticalindustry in blister packaging and nonmedicaments that are user-friendlyto patients and other users of the package. It can provide an attractiveand inexpensive package for the merchandising of pharmaceutical andother products that is constructed in a manner that facilitates massproduction. The packages may contain one to a multiplicity of articles,such as food, medicaments in the form of capsules, tablets, medicalinstruments, syringes, lozenges, pills and/or the like, ornonmedicaments, such as poisons, catalysts, cleaning compositions,batteries, and other goods that need to be protected from oxygen andmoisture.

Films comprising the compositions of this invention can be made byvirtually any method known to one skilled in this art. The film can beeither a single layer or multilayer polymeric film. As such, the filmand film structures can be typically cast, extruded, co-extruded,laminated, and the like, including orientation (either uniaxially orbiaxially) by various methodologies (e.g., blown film, mechanicalstretching or the like).

The invention further directs to a monolayer, or multilayer coextrudedor laminated structure that involves the adhesive described herein as alayer, typically a heat seal layer, to provide a bond between otherpackaging components. The peel seal strength of these compositionsallows for bonding of various lidding substrates, including substratesmade from ethylene vinyl acetate, polyethylene, polystyrene,polypropylene, polyethylene terephthalate, polyvinyl chloride, metalssuch as aluminum, spun-bonded polyolefins such as TYVEK® (commerciallyavailable from DuPont), oriented polyesters such as MYLAR® (DuPont), andthe like, can be adjusted by varying the amount and type ofethylene/(meth)acrylate copolymer, polyolefin content tackifier and/orfiller in the adhesive composition.

The invention also provides a multilayer structure comprising at leastone layer prepared from a composition disclosed herein and at least oneadditional layer comprising foil, paper, polyester, polyamide,polyolefin, polyethylene vinyl alcohol, polyethylene vinyl acetate,ethylene/(meth)acrylic acid copolymer and ionomer thereof, polyvinylchloride, polyvinylidene chloride, and anhydride-modified polyolefin.Multilayer structures of note comprise at least one layer of thecompositions of note as defined above. Preferred structures comprise atleast one layer of the preferred compositions as defined above.

The multilayer polymeric sheet can involve at least three categoricallayers including, but not limited to, an outermost structural or abuselayer, an inner barrier layer, bulking layer and/or adhesive layer, andan innermost layer making contact with and compatible with the intendedcontents of the package and capable of forming the necessary seals (e.g.most preferably heat-sealable) to itself and the other parts of thepackage. Other layers may also be present to serve as adhesive or “tie”layers to help bond these layers together.

The outermost structural or abuse layer can be oriented polyester ororiented or non-oriented polypropylene, but can also include oriented ornon-oriented polyamide (nylon) or polyethylene such as HDPE or paper orfoil. This layer, when optically transparent, preferably is reverseprintable and unaffected by the sealing temperatures used to make thepackage, since the package is sealed through the entire thickness of themultilayer structure. When the outer structural or abuse layer is notoptically transparent, this layer can be surface printed and thenoptionally coated with a protective coating or lacquer. The thickness ofthis layer can control the stiffness of the film, and may range fromabout 10 to about 100 μm or from about 12 um to about 50 μm.

The inner layer can include one or more barrier layers, depending onwhich atmospheric conditions (oxygen, humidity, light, and the like)that potentially can affect the product inside the package. Barrierlayers can be, for example, metallized PP or PET), polyethylene vinylalcohol (EVOH), polyvinyl alcohol, polyvinylidene chloride, polyolefins,aluminum foil, nylon, blends or composites of the same as well asrelated copolymers thereof. Barrier layer thickness may depend onfactors such as the sensitivity of the product and the desired shelflife.

The inner layer can include one or more bulking layers. This layer isusually added to create a structure that has a final, predefinedthickness by using a common polymer that is of low cost. Bulking layerscan be, for example, polyolefin, polyolefin polar copolymer, polyesterand or blends of various bulking layer components. A bulking layer isalso suitable for incorporation of regrind and scrap generated in themanufacturing process. For example, scrap generated from material that,for one reason or another, is not suitable for sale, or material that isgenerated by trimming the edges off a semi-finished roll, can be groundup and incorporated into the inner layer providing bulk at relativelylow cost.

The inner layer can include one or more adhesive layers. This adhesivelayer is usually designed to adhere the outer structural layer to theinner layer, the inner layer to the innermost layer or, in the casewhere the inner layer may only be acting as an adhesive, bonding theouter layer directly to the innermost layer.

The innermost layer can be the sealant layer, which can be prepared fromthe composition disclosed above.

The structure and barrier layers can be combined to comprise severallayers of polymers that provide effective barriers to moisture andoxygen and bulk mechanical properties suitable for processing and/orpackaging the product, such as clarity, toughness andpuncture-resistance. In some applications, the functions of structureand barrier layers may be combined in a single layer of a suitableresin. For example, nylon or PET are suitable for both structure andbarrier functions.

Polyamides include aliphatic polyamides, amorphous polyamides, or amixture thereof. Aliphatic polyamides can refer to aliphatic polyamides,aliphatic copolyamides, and blends or mixtures of these such aspolyamide 6, polyamide 6.66, blends and mixtures thereof. Polyamides6.66 are commercially available under the tradenames “Ultramid® C4” and“Ultramide C35” from BASF, or under the tradename “Ube®5033FXD27” fromUbe Industries Ltd. Polyamide 6 can be commercially available under thetradename Capron® from Honeywell International.

The film may further comprise other polyamides such as those disclosedin U.S. Pat. Nos. 5,408,000; 4,174,358; 3,393,210; 2,512,606; 2,312,966and 2,241,322.

The film may also comprise partially aromatic polyamides such as theamorphous nylon resins 6-1/6-T commercially available under thetradename Selar® PA from DuPont or commercially available under thetradename Grivory® G 21 from EMS-Chemie AG.

Ionomers are copolymers of an olefin such as ethylene and an unsaturatedcarboxylic acid, such as acrylic acid or methacrylic acid and optionallysoftening monomers wherein at least one or more alkali metal, transitionmetal, or alkaline earth metal cations, such as sodium, potassium orzinc, are used to neutralize some portion of the acidic groups in thecopolymer, resulting in a thermoplastic resin exhibiting enhancedproperties. For example, “Ethylene/(meth)acrylic acid (E/(M)AA)” means acopolymer of ethylene (E)/acrylic acid (AA) and/or ethylene/methacrylicacid (MAA) which are at least partially neutralized by one or morealkali metal, transition metal, or alkaline earth metal cations to forman ionomer. Terpolymers can also be made from an olefin such asethylene, an unsaturated carboxylic acid and other comonomers such asalkyl (meth)acrylates to provide “softer” resins that can be neutralizedto form softer ionomers. Ionomers are known conventionally and theirmethod of preparation is disclosed in, for example, U.S. Pat. No.3,344,014.

Anhydride or acid-modified ethylene and propylene homo- and co-polymerscan be used as extrudable adhesive layers (also known as “tie” layers)to improve bonding of layers of polymers together when the polymers donot adhere well to each other, thus improving the layer-to-layeradhesion in a multilayer structure. The compositions of the tie layerscan depend on the compositions of the adjoining layers that need to bebonded in a multilayer structure. One skilled in the polymer art canselect the appropriate tie layer based on the other materials used inthe structure. Various tie layer compositions are commercially availableunder the tradename Bynel® from DuPont.

EVOH having from about 20 to about 50 mole % ethylene can be used.Suitable polyethylene vinyl alcohol copolymers are commerciallyavailable under the tradename EVAL® from Kuraray or commerciallyavailable under the tradename Soarnol® from Nippon Goshei.

PVDC polymers and copolymers suitable for use herein as coatings orfilms can be obtained commercially from Dow Chemical under the tradenameSaran®, for example.

The manufacture of a film used in this invention from the compositionsdisclosed above can be carried out according to any known methods. It ispossible, for example, to manufacture a primary film by extruding thecompositions using so-called “blown film” or “flat die” methods. A blownfilm can be prepared by extruding a polymer composition through anannular die and expanding the resulting tubular film with an air currentto provide a blown film. Cast flat films can be prepared by extruding acomposition through a flat die. The film leaving the die is cooled by atleast one roll containing internally circulating fluid (a chill roll) orby a water bath to provide a cast film. The film can be sized byconventional techniques such as slitting to provide a packaging film.

A film can be further oriented beyond the immediate quenching or castingof the film. The process comprises the steps of extruding a laminar flowof molten polymer, quenching the extrudate and orienting the quenchedextrudate in at least one or more directions. “Quenched” describes anextrudate that has been substantially cooled below its melting point inorder to obtain a solid film material.

The film can be unoriented, oriented in a uniaxial direction (e.g.machine direction), or oriented in a biaxial direction (e.g. machinedirection and transverse direction). The film can be biaxially orientedby drawing in two mutually perpendicular directions in the plane of thefilm to achieve a satisfactory combination of mechanical and physicalproperties.

Orientation and stretching apparatus to uniaxially or biaxially stretchfilm are known in the art and may be adapted by those skilled in the artto produce films of the present invention. See, e.g., U.S. Pat. Nos.3,278,663; 3,337,665; 3,456,044; 4,590,106; 4,760,116; 4,769,421;4,797,235 and 4,886,634.

A blown film may be oriented using a double bubble extrusion process,where simultaneous biaxial orientation may be effected by extruding aprimary tube which is subsequently quenched, reheated and then expandedby internal gas pressure to induce transverse orientation, and drawn bydifferential speed nip or conveying rollers at a rate which may inducelongitudinal orientation.

The processing to obtain an oriented blown film is known in the art as adouble bubble technique, and can be carried out as disclosed in U.S.Pat. No. 3,456,044. A primary tube can be melt extruded from an annulardie. This extruded primary tube can be cooled quickly to minimizecrystallization. It can be then heated to its orientation temperature(for example, by means of a water bath). In the orientation zone of thefilm fabrication unit a secondary tube is formed by inflation, therebythe film is radially expanded in the transverse direction and pulled orstretched in the machine direction at a temperature such that expansionoccurs in both directions, preferably simultaneously; the expansion ofthe tubing being accompanied by a sharp, sudden reduction of thicknessat the draw point. The tubular film is then again flattened through niprolls. The film can be reinflated and passed through an annealing step(thermofixation), during which step it is heated once more to adjust theshrink properties.

The film can be formed by an extrusion process that causes the polymerchains in the film to be generally aligned in the direction ofextrusion. Linear polymers, after being highly oriented uniaxiallypossess considerable strength in the orientation direction, but lessstrength in the transverse direction. This alignment can add strength tothe film in the direction of extrusion.

The films may or may not be treated by means of corona discharge, ozoneor other means standard in the industry.

The seal strength of the multilayer structure to the container candepend on the thickness of the ethylene copolymer-polyolefin heat seallayer. The thickness of the heat seal layer can be between about 10 and40 μor about 10 to 30 μm.

The multilayer structures can be useful in a variety of packagingapplications as packaging materials. They may also be used as industrialfilms such as masking films whereby a film is thermally laminated to asubstrate, such as foil or polyester or acrylic, and peeled off whensurface protection is no longer required.

The packaging materials may also be processed further by, for examplebut not limited to, printing, embossing, and/or coloring to provide apackaging material to provide information to the consumer about theproduct therein and/or to provide a pleasing appearance of the package.

Some examples of multilayer film structures of this invention are listedbelow in which the sealant layer can be prepared from an ethylenecopolymer-polyolefin composition disclosed above and wherein “adh”refers to an adhesive system as described above, “tie” refers to anextrudable adhesive or tie layer, and “Ink” refers to the printingdescribed above.

Multilayer film structures include blown films having the structuresindicated:

-   -   Polyamide (Nylon)/tie/EVOH/tie/Sealant; or    -   PP/tie/EVOH/tie/Sealant.

Multilayer film structures include adhesive laminated films having thestructures indicated:

-   -   Ink/Foil/adh/PE/PE/Sealant; or    -   PET/Ink/adh/PE/tie/EVOH/tie/Sealant.

Multilayer film structures include extrusion-coated films having thestructures indicated:

-   -   Ink/Foil/tie/Sealant;    -   PET/PVDC/Ink/tie/Sealant;    -   Ink/PET/tie/Sealant;    -   Ink/Paper/PE/Sealant.

Multilayer film structures include extrusion-laminated films having thestructures indicated:

-   -   PET/PVDC/Ink/tie/Sealant;    -   PET/adh/Sealant; or    -   PET/adh/Nylon/tie/Sealant.

The multilayer structures described above may be incorporated intopackages, such as lidded containers, by standard methods well known inthe art. The multilayer structures can be useful as lidding materialsfor containers. Packages or containers include molded, pressed orthermoformed containers comprising a structure and/or multilayerstructures disclosed above. In addition to the materials listed above,the rigid containers may contain other materials such as, for example, apolymeric resin modified by various additives to provide a modifiedpolymeric blend suitable for preparing containers, such as toughenedCPET. The materials can also be modified with other additives such asdenesting agents and can also be modified with additives such asfillers. The containers can be multilayer containers containing aninnermost product contact layer, an inner layer that can be a barrier orbulking layer and an outer or abuse layer.

Such containers may be used to package products such as yogurts,puddings, custards, gelatins, fruit sauces (for example, applesauce) andthe like. They may also be used to package cheese spreads and dips.Packages as described herein may also be used as packages for meats andfrozen or refrigerated meals. Packages of this invention also includepackages for dry foods such as noodles and seasoning for reconstitutionwith water. They can also be used to package dry snacks such as cookies,chips and the like.

The following Examples are merely illustrative, and are not to beconstrued as limiting the scope of the invention.

EXAMPLES

Compositions were prepared from the materials listed below usingstandard blending techniques to provide Examples 1 through 20compositions summarized in Tables 1 through 3 below. ComparativeExamples were prepared similarly using the materials listed below.

Materials Used

-   EMA-7: An ethylene/(meth)acrylate (9 weight %) copolymer with MI of    6 available from DuPont.-   EMA-8: An ethylene/(meth)acrylate (20 weight %) copolymer with MI of    8 available from DuPont.-   EMA-9: An ethylene/(meth)acrylate (13 weight %) copolymer with MI of    9 available from DuPont.-   PE-1: A copolymer of ethylene and 1-butene with MI of 3.5 (available    as Exact® 3035 from ExxonMobil).-   PE-2: A copolymer of ethylene and 1-octene (12 weight % octane) with    MI of 3.5 (available as Engage® 8450 from DuPont Dow Elastomers).-   Add-1: 2 weight % of silicon dioxide dispersion in an    ethylene/methacrylic acid copolymer (available from DuPont as    Conpol® 20S2).-   Tack-1: A tackifier resin derived from poly-limonene available as    Piccolyte® C115 from Pinova.-   Tack-2: A tackifier resin available as Regalite R1125 from Eastman.-   Filler-1: A blend of 50 weight % of talc and 50 weight % of EMA-8.-   Antiox-1: Antioxidant Irganox® 1010.-   EVA-1: An ethylene/vinyl acetate (7 weight %) copolymer with MI of 7    available from DuPont.-   EVA-2: An ethylene/vinyl acetate (17 weight %) copolymer with MI of    30 available from DuPont.-   EVA-3: An ethylene/vinyl acetate (12 weight %) copolymer with MI of    8 available from DuPont.-   EVA-4: An ethylene/vinyl acetate (25 weight %) copolymer with MI of    25 available from DuPont.-   EVA-5: An ethylene/vinyl acetate (17 weight %) copolymer with MI of    30 available from DuPont.-   Ionomer-1: An ethylene/methacrylic acid copolymer partially    neutralized with zinc with MI of 14 available from DuPont.

In Tables 1 through 3, amounts listed as parts by weight and “- -” meansa component is not present in the composition. TABLE 1 Ex. EMA copolymerPE-1 Tack-1 Add-1 Antiox-1 1 EMA-7 52.95 30 15 2 0.05 2 EMA-7 62.95 2015 2 0.05 3 EMA-7 42.95 40 15 2 0.05 4 EMA-9 52.95 30 15 2 0.05 5 EMA-967.95 30 — 2 0.05 6 EMA-7 67.95 30 — 2 0.05 7 EMA-9 82.95 — 15 2 0.05

TABLE 2 co- Ex. EMA polymer PE-2 Tack-1 Add-1 Filler-1 Antiox-1  8 EMA-750.95 27.5 15 1.5 5 0.05  9 EMA-7 45.45 23 15 1.5 15 0.05 10 EMA-7 42.9520.5 15 1.5 20 0.05 11 EMA-7 40.45 18 15 1.5 25 0.05 C12 EMA-9 78.50 — —1.5 20 — C13 EMA-9 73.50 — — 1.5 25 — C14 EMA-9 68.50 — — 1.5 30 — C15EMA-9 64.50 — — 1.5 35 — 16 EMA-7 52.95 30 15 2 — 0.05 30 EMA-7 52.9526.25 18.75 2 — 0.05 31 EMA-7 35.45 14.3 15.2 — 35 0.05

TABLE 3 co- Ex. EMA polymer PE-1 Tack-1 Add-1 Filler-1 Antiox-1 C17EMA-9 85 — — — 15 — C18 EMA-9 88 — — 2 10 — C19 EMA-9 83 — — 2 15 — 20EMA-9 47.95 25 15 2 10 0.05

Table 4 summarizes some heat seal compositions known in the art. Theycan be described generally as compositions comprising (a) from 20 to 90parts by weight of at least one ethylene/vinyl acetate copolymer; (b)from 10 to 50 parts by weight of at least one polyolefin; (c) from 1 to40 parts by weight of at least one tackifying resin; and (d) from 0 toabout 50 parts by weight of filler. TABLE 4 Comparative ComparativeExample C1 Weight % Example C2 Weight % EVA-1 40 EVA-1 40 PE-1 40 PE-240 Tack-2 20 Tack-2 20 Comparative Comparative Example C3 Weight %Example C4 Weight % EVA-1 52 EVA-1 52 PE-1 35 PE-2 35 Tack-1 10 Tack-110 EVA-2 3 EVA-2 3 Comparative Comparative Example C5 Example C6 EVA-149.95 EVA-1 49.95 PE-1 30 PE-2 30 Tack-1 15 Tack-1 15 EVA-2 5 EVA-2 5Antiox-1 0.05 Antiox-1 0.05 Comparative Comparative Example C7 ExampleC8 EVA-3 54.95 EVA-3 54.95 PE-1 30 PE-2 30 Tack-1 15 Tack-1 15 Antiox-10.05 Antiox-1 0.05

Table 5 summarizes some physical properties of the heat sealcompositions described herein. Inspection of Table 5 shows thatcompositions have physical properties that are very similar to those ofknown heat seal compositions. TABLE 5 Composition Melt Index Meltingpoint Vicat softening point Comp. Ex. C1 8 94 68 Comp. Ex. C2 8 97 67.7Comp. Ex. C3 6.9 95 72 Comp. Ex. C4 6.0 95.5 70.7 Comp. Ex. C5 8.6 93 66Comp. Ex. C6 9.7 94 67.5 Comp. Ex. C7 8.6 93 66 Comp. Ex. C8 10.3 9165.9 Example 1 7.1 93 64 Example 16 7.3 97 65.9

Tests Employed in Examples

Melt Index (MI) was measured in accord with ASTM D-1238, condition E, at190° C., using a 2160-gram weight, with values of MI reported in g/10minutes. Density was determined in accord with ASTM D-792. Melting point(m.p.) was determined by differential scanning calorimetry (DSC) inaccord with ASTM D-3418. Vicat softening point was determined in accordwith ASTM D-1525.

Peel Strength: Seal layers were sealed to substrates using standardsealing equipment and conditions to provide one-inch wide sealed strips.The layers were separated at the seal layer/substrate interface unlessotherwise noted and pulled in a tensile tester at room temperature in a“T-peel” configuration at a separation speed of 12 inches/minute. Theaverage force required to separate the layers divided by the width isreported as the peel strength (g/inch). Typically, three to fiveseparate determinations were averaged together and reported in theTables.

The mode of failure reported in Tables 6 through 10 is characterized bythe following descriptors:

-   -   “P”—peels cleanly away from the substrate    -   “FT”—film tear (shredding)    -   “FB”—film break    -   “CL”—coating lift    -   “ZP”—zipper peel    -   “T”—tack    -   “NT”—no tack    -   “D”—delamination

Table 6 provides peel data (g/inch, room temperature, 50% relativehumidity, average of three repetitions) for a monolayer film comprisingthe composition of Example 6 sealed to several substrates at theindicated temperatures having one inch seal width, prepared using aSentinel sealer at 40 psi with a dwell time of one second. TABLE 6 SealStrength (g/inch) Failure Seal Temperature ° F. 250 300 350 400 ModeCrystallized Polyethylene 993 1193 1667 1983 P terephthalatePolypropylene homopolymer 843 1450 3666 3383 P High-impact polystyrene757 1067 1100 1233 P

Example 21

A multilayer lidding material of this invention, comprising a 2.0mil-thick outer layer of foil, a 0.5 mil-thick middle layer of anethylene acid copolymer having 12 weight % methacrylic acid and a MI of13.5 (available from DuPont as Nucrel® 1214), and a 1.0 mil-thick innerseal layer of the composition of Example 1, was prepared using standardlamination techniques. Table 7 provides peel data (g/inch, average offive repetitions) for the multilayer lidding material of Example 21sealed to several substrates at the indicated temperatures. The sealswere prepared using a Sentinel sealer at 40 psi with a dwell time of onesecond to provide a one-inch seal width. TABLE 7 Failure SealTemperature ° F. 250 300 350 400 Mode Seal Strength (g/inch)Crystallized Polyethylene 2385 3060 2974 3133 P terephthalatePolypropylene homopolymer 1431 2293 3261 3298 P High-impact polystyrene1712 1179 1269 1306 P After holding at 32° F. for 3 days CrystallizedPolyethylene 1981 2486 3113 3092 P terephthalate Polypropylenehomopolymer  543  631 4185 3918 P High-impact polystyrene 3566 3985 43334089 P P/D(1) P/D(1)

Comparative Example 22

A multilayer lidding material, comprising a 1.0 mil-thick outer layer ofamorphous polyester (available as Mylar LBT from DuPont Teijin Films), a1.0 mil-thick layer of high density polyethylene, a 0.5 mil-thick layerof a blend of high density polyethylene and low density polyethylene,and a 0.5 mil-thick inner seal layer of the composition of ComparativeExample C6, was prepared using standard lamination techniques. Table 8provides peel data (g/inch, average of five repetitions) for thismultilayer lidding material sealed to substrates at the indicatedtemperatures for comparison to Example 21. The seals were prepared usinga Sentinel sealer at 40 psi with a dwell time of one second to provide aone-inch seal width. TABLE 8 Failure Seal Temperature ° F. 250 300 350400 Mode Seal Strength (g/inch) Crystallized Polyethylene  763 1111 10181072 P terephthalate Polypropylene homopolymer  831 1489 2695 2913 PHigh-impact polystyrene  545  735  771  741 P After holding at 32° F.for 3 days Crystallized Polyethylene 1212 1272  867  828 P terephthalatePolypropylene homopolymer 104 T  293  852  905 P High-impact polystyrene1078 1415 1393 1013 P

Comparison of the data in Tables 7 and 8 shows that the inventioncompositions, when used as a sealant layer, provided stronger, yet stillpeelable seals than a known sealant and exhibited less reduction in sealstrength when held at freezing temperatures.

Example 23 and Comparative Examples 24-26

A film comprising the composition of Example 4 was prepared and heatsealed to a film comprising PCTFE. The seals were prepared using aSentinel sealer at 40 psi with a dwell time of one second to provide aone-inch seal width.

Table 9 provides peel data (average of 25 repetitions) at roomtemperature and 50% relative humidity for Example 23. ComparativeExamples in Table 9 are lidding materials based on solvent coatings.

Comparative Example C24 is a solvent coating based on styrene butadieneand Comparative Example C25 is a solvent coating based on amorphouspolyester. Both materials are available from Hueck Folien of Germany.TABLE 9 Temperature Sample 250° F. 300° F. 350° F. 400° F. Failure ModeC24 0 0 227 372 25P Ex. 23 1342 1440 1574 2504 25P (prepared fromExample 4) C25 1328 1669 1719 1781 23P, 2D C26 982 953 950 1051 25P

Inspection of the data in Table 9 shows that Comparative Example C24provided low strength peelable seals. Comparative Example C25 providedseals of adequate strength, but incidences of delamination indicated thepotential for contamination of the product with packaging material.Example 23 provided good strength seals with consistently clean peelseals.

Comparative Example 27 and Example 28

A film prepared according to the description for Example 23 andheat-sealed to a film comprising PCTFE. The PCTFE film was previouslythermoformed into blister pack blanks using a Medipak Model CP-21packaging machine (upper and lower forming temperatures 115° C.). Theexample films were heat-sealed to the PCTFE face of the formed film atvarious temperatures at a seal pressure of 2,500 psi and 25 cpm(containers per minute).

Table 10 provides peel data (average of 5 repetitions) at roomtemperature and 50 % relative humidity. Comparative Example C27 used afilm comprising the blend used in Comparative Example C26 (Table 9).Although Table 10 indicates that C26 sealed adequately to PCTFE usinghigher temperatures, it did not seal to the PCTFE film at these lowsealing temperatures. Example 28 films heat-sealed and peeled cleanlyfrom the PCTFE film, even using low sealing temperatures. TABLE 10Comparative Example C27 Ex. 28 Composition of heat seal layer C26 Ex. 4Seal Temperature ° C. Average Seal Strength (Grams/0.75 inch)¹ 125 17.7(no seal) 920 150 17.7 (no seal) 841 175 17.7 (no seal) 952 200 17.7 (noseal) 983¹Nominal width of blister pack heat-seal.

Examples 32-36

Compositions were prepared by blending the materials listed in Tables 11and 12 using standard blending techniques of dry blending followed bymelt compounding. A melt-blend of 80 weight % of Tack-1 and 20 weight %of PE-2 was used as the source of Tack-1 (with supplemental PE-2) inthese compositions (the amounts reported for those components in Tables11 and 12 are the total amounts after incorporation of the pre-blend).TABLE 11 Ex. EMA copolymer PE-2 Tack-1 PE-3 Filler-1 Antiox-1 32 EMA-724.95 13 12 25 25 0.05 33 EMA-7 14.95 18 12 25 30 0.05 34 EMA-7 14.95 1312 30 30 0.05

TABLE 12 Ex. EMA copolymer PE-2 Tack-1 PE-3 Filler-2 Antiox-1 35 EMA-734.95 18 12 25 10 0.05 36 EMA-7 34.95 13 12 25 15 0.05

1. A composition consisting essentially of (A) from about 10 to about 80weight % of at least one ethylene/alkyl (meth)acrylate copolymer; fromabout 5 to about 60 weight % of at least one polyolefin; from 0 to about35 weight % of at least one tackifying resin; and from 0 to about 35weight % of filler (B) from about 10 to about 80 weight % of at leastone ethylene/alkyl (meth)acrylate copolymer; from about 5 to about 60weight % of at least one polyolefin; from 0 to about 35 weight % of atleast one tackifying resin; and from 0 to about 30 weight % of filler;or (C) from about 40 to about 80 weight % of at least one ethylene/alkyl(meth)acrylate copolymer; and from about 20 to about 60 weight % of atleast one polyolefin.
 2. The composition of claim 1 consistingessentially of from about 10 to about 80 weight % of at least oneethylene/alkyl (meth)acrylate copolymer; from about 5 to about 60 weight% of at least one polyolefin; from about 0.5 to about 35 weight % of atleast one tackifying resin; and from 0 to about 30 weight % of filler.3. The composition of claim 1 consisting essentially of from about 40 toabout 80 weight % of at least one ethylene/alkyl (meth)acrylatecopolymer; from about 20 to about 60 weight % of at least onepolyolefin; and from about 10 to about 20 weight % of at least onetackifying resin.
 4. The composition of claim 1 consisting essentiallyof from about 40 to about 60 weight % of at least one ethylene/alkyl(meth)acrylate copolymer; from about 20 to about 40 weight % of at leastone polyolefin; from about 10 to about 20 weight % of at least onetackifying resin; and from about 5 to about 20 weight % of a filler. 5.The composition of claim 1 wherein the ethylene/alkyl (meth)acrylatecopolymer comprises repeat units derived from 5 to 30 weight % of alkyl(meth)acrylate.
 6. The composition of claim 3 wherein the alkyl group inthe alkyl (meth)acrylate has from one to four carbon atoms.
 7. Thecomposition of claim 4 wherein the alkyl (meth)acrylate is methylacrylate.
 8. The composition of claim 7 wherein the ethylene/alkyl(meth)acrylate copolymer comprises repeat units derived from 9 to 24weight % of the methyl acrylate.
 9. The composition of claim 1 whereinthe ethylene/(meth)acrylate copolymer has a melt index from about 0.1 toabout 100 g/10 minute or about 0.5 to about 50 g/l 0 minute and theethylene/(meth)acrylate copolymer comprises two differentethylene/methyl acrylate copolymers.
 10. The composition of claim 1wherein the filler is an inorganic mineral or salt.
 11. The compositionof claim 4 wherein the filler is talc.
 12. The composition of claim 4wherein the filler is a polymeric material that is not fully compatiblewith the ethylene/alkyl (meth)acrylate, the polyolefin of component, orboth.
 13. The composition of claim 12 wherein the filler is apolystyrene.
 14. The composition of claim 3 wherein the ethylene/alkyl(meth)acrylate copolymer comprises repeat units derived from maleicanhydride, glycidyl methacrylate, carbon monoxide, or combinations oftwo or more thereof.
 15. The composition of claim 4 wherein theethylene/alkyl (meth)acrylate copolymer comprises repeat units derivedfrom maleic anhydride, glycidyl methacrylate, carbon monoxide, orcombinations of two or more thereof.
 16. The composition of claim 15wherein the filler is a polystyrene.
 17. The composition of claim 1wherein the polyolefin is polyethylene homopolymer, polypropylenehomopolymers, copolymer comprising ethylene, copolymer comprisingpropylene, or combinations of two or more thereof.
 18. The compositionof claim 17 wherein the polyolefin is a copolymer of ethylene and1-butene, 1-hexene, 1-octene, or combinations of two or more thereof.19. The composition of claim 3 wherein the tackifying resin of iscoumarone-indene resin, terpene resin, butadiene-styrene resin,hydrocarbon resin, rosin material, or combinations of two or morethereof.
 20. The composition of claim 4 wherein the tackifying resin isderived from poly-limonene.
 21. The composition of claim 1 wherein theethylene/(meth)acrylate copolymer is prepared in a tubular reactor. 22.The composition of claim 3 wherein said ethylene/(meth)acrylatecopolymer is prepared in a tubular reactor.
 23. The composition of claim4 wherein said ethylene/(meth)acrylate copolymer is prepared in atubular reactor.
 24. The composition of claim 17 wherein saidethylene/(meth)acrylate copolymer is prepared in a tubular reactor. 25.The composition of claim 19 wherein said ethylene/(meth)acrylatecopolymer is prepared in a tubular reactor.
 26. A multilayer structurecomprising at least one layer comprising or produced from a composition,at least one second layer, and optionally at least one third layerwherein the composition is as recited in claim 1; the second layercomprises or is produced from of foil, paper, polyester, polyamide,polyolefin, polyethylene vinyl alcohol, polyethylene vinyl acetate,ethylene/(meth)acrylic acid copolymer, and ionomers ofethylene/(meth)acrylic acid copolymer, polyvinyl chloride,polyvinylidene chloride, or anhydride-modified polyolefin; and the thirdlayer comprises or is produced from foil, paperboard, glass,high-density polyethylene polypropylene, polystyrene or high-impactpolystyrene, expanded polystyrene, acrylic homopolymer, acryliccopolymer, polycarbonate, polysulfone, amorphous polyethyleneterephthalate, crystalline polyethylene terephthalate, PVC,polychlorotrifluoroethylene, polyacrylonitrile homopolymer,polyacrylonitrile copolymer, polyacetal, or polyacetal copolymer. 27.The multilayer of claim 26 wherein the composition is as recited inclaim
 3. 28. The multilayer of claim 26 wherein the composition is asrecited in claim
 4. 29. The multilayer of claim 26 wherein thecomposition is as recited in claim
 24. 30. The multilayer of claim 26wherein the composition is as recited in claim
 25. 31. The multilayer ofclaim 26 being used as a lidding material for containers.
 32. Themultilayer of claim 27 being used as a lidding material for containers.33. The multilayer of claim 28 being used as a lidding material forcontainers.
 34. The multilayer of claim 29 being used as a liddingmaterial for containers.
 35. The multilayer of claim 30 being used as alidding material for containers.
 36. The multilayer of claim 26 furthercomprising or produced from the third layer.
 37. The multilayer of claim27 further comprising or produced from the third layer.
 38. Themultilayer of claim 28 further comprising or produced from the thirdlayer.
 39. The multilayer of claim 29 further comprising or producedfrom the third layer.
 40. The multilayer of claim 30 further comprisingor produced from the third layer.
 41. A package or container comprisingor produced from a composition or a multilayer structure wherein thecomposition is as recited in claim
 1. 42. The package or container ofclaim 41 wherein the package or container comprises or is produced fromthe composition, which is as recited in claim
 2. 43. The package orcontainer of claim 42 wherein the composition is as recited in claim 3.44. The package or container of claim 42 wherein the composition is asrecited in claim
 4. 45. The package or container of claim 42 wherein thecomposition is as recited in claim
 24. 46. The package or container ofclaim 42 wherein the composition is as recited in claim
 25. 47. Thepackage or container of claim 41 wherein the package or containercomprises or is produced from the multilayer, which is as recited inclaim
 26. 48. The package or container of claim 47 wherein themultilayer is as recited in claim
 27. 49. The package or container ofclaim 47 wherein the multilayer is as recited in claim
 28. 50. Thepackage or container of claim 47 wherein the multilayer is as recited inclaim
 29. 51. The package or container of claim 47 wherein themultilayer is as recited in claim
 30. 52. The package or container ofclaim 47 wherein the multilayer is as recited in claim
 36. 53. Thepackage or container of claim 47 wherein the multilayer is as recited inclaim
 37. 54. The package or container of claim 47 wherein themultilayer is as recited in claim
 38. 55. The package or container ofclaim 47 wherein the multilayer as recited in claim
 39. 56. The packageor container of claim 47 wherein the multilayer is as recited in claim40.
 57. The package or container of claim 41 comprising the containerand a peelable lid comprising a multilayer structure as recited in claim26.
 58. The package or container of claim 57 wherein the multilayer isas recited in claim
 36. 59. The package or container of claim 57 whereinthe second layer comprises a polychlorotrifluoroethylene fluoropolymer.60. The package or container of claim 57 being a blister package, apouch, a molded, a pressed or thermoformed container.